JP7208575B2 - Assemblies and fragrance products - Google Patents

Description

The present disclosure relates to an assembly in which a tube is fixed to a molded body, and this assembly can be attached to, for example, an opening of a container and used as an assembly for injecting liquid in the container. The present disclosure also relates to fragrance products that can be used to jet liquid fragrances.

Spray pumps and dispenser pumps are used to eject liquid fragrances. For example, U.S. Pat. No. 6,200,000 discloses a fragrance product that includes a container and dispenser assembly. In the fragrance product described in U.S. Patent No. 6,000,008, the dispenser assembly comprises a transport assembly including a pump for transporting the liquid fragrance from the interior of the container to the exterior of the container for application to the individual; It has a tube that extends to the

JP 2014-12185 A

An object of the present disclosure is to provide an assembly in which a tube can be easily fixed to a molded body.

According to the present disclosure, an assembly comprising a tube for circulating a liquid having a refractive index of 1.35 to 1.41, and a molded body provided with a fitting portion for fitting one end of the tube, , the molded body is formed of a non-fluoropolymer, the tube is formed of a fluoropolymer having a tensile elastic modulus of 300 MPa or more, and the non-fluoropolymer has a tensile elastic modulus of 1 Assemblies are provided that have a tensile modulus of .2 or more.

The assembly of the present disclosure further includes an injection device for injecting a liquid having a refractive index of 1.35 to 1.41, the injection device inserting the molded body into a fitting for fitting one end of the tube. It is preferably provided as a holding member provided with an attachment portion.

Preferably, the fluoropolymer has a refractive index of 1.35 to 1.41.
The haze value of the fluoropolymer is preferably 30% or less.
It is preferable that the fluoropolymer has a transmittance of 50% or more for light having a wavelength of 400 nm.
The tube is preferably made of at least one fluoropolymer selected from the group consisting of copolymers containing ethylene units and tetrafluoroethylene units, and polymers containing vinylidene fluoride units. .
It is preferable that the tube is made of two or more fluoropolymers having different monomer compositions.
Preferably, the tube is insoluble in acetone.
The molded article is preferably made of at least one non-fluoropolymer selected from the group consisting of polyolefins and polyesters.
It is preferable that unevenness is provided on the inner peripheral surface of the fitting portion of the molded body.
It is preferable that the inner diameter of the fitting portion of the molded body is smaller than the outer diameter of the tube by 0.5% or more.
It is preferable that at least one end of the tube is provided with a notch.

Also according to the present disclosure, there is provided a fragrance product comprising an assembly as described above and a container body.

According to the present disclosure, it is possible to provide an assembly that can easily fix a tube to a molded body.

FIG. 1 is a schematic diagram showing one embodiment of a spray can with assembly. FIG. 2 is a schematic cross-sectional view showing one embodiment of a connection structure between a holding member (molded body) and a tube of an injection device. FIG. 3 is a schematic diagram showing one embodiment of a tube.

Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

FIG. 1 shows an embodiment of a spray container capable of manually spraying a predetermined amount of liquid. The spray container 10 shown in FIG. 1 comprises a container body 11 , an assembly comprising an injection device 20 and a tube 30 , and a liquid 12 contained in the container body 11 . The injection device 20 is attached so as to seal the container body 11 . The injection device 20 is provided with an injection pump, and when the injection button 21 is pushed down, the liquid 12 sucked up through the tube 30 is injected from the injection port 22 .

FIG. 2 is a schematic cross-sectional view showing one embodiment of a connection structure between an injection device and a tube in a spray container. As shown in FIG. 2, the injection device 20 comprises a holding member 23 directly or indirectly connected to the injection pump, and the holding member 23 comprises a molding made of a non-fluoropolymer. . Further, the holding member 23 is provided with a fitting portion 24 to which one end of the tube 30 is fitted.

US Pat. No. 5,300,003 discloses a dispenser assembly comprising a tube connected to a transport assembly and extending into a liquid fragrance. A problem with such conventional arrangements, however, is that it is difficult to attach a tube to the transport assembly for supplying the liquid fragrance to the transport assembly. Accordingly, an assembly is desired that allows the tube to be easily secured to the injector.

In the connection structure shown in FIG. 2 , one end of the tube is fitted to fitting portion 24 of holding member 23 . The non-fluoropolymer of the molding forming the holding member 23 has a tensile elastic modulus 1.2 times or more that of the fluoropolymer of the tube 30, and moreover, the tensile elastic modulus of the fluoropolymer. is 300 MPa or more, the tube 30 is not bent when one end of the tube 30 is fitted into the fitting portion 24 of the holding member 23 . Moreover, when the one end of the tube 30 is inserted into the fitting portion 24 of the holding member 23 , the one end of the tube 30 is elastically deformed, so that the outer peripheral surface 31 of the tube 30 is pulled from the fitting portion 24 of the holding member 23 . is pressed against the inner peripheral surface 25 of the . According to the assembly of the present disclosure, the tube 30 can be easily fixed to the injection device 20 as described above.

The holding member 23 of the injection device 20 is composed of a molding made of a non-fluoropolymer. The non-fluoropolymer is not limited as long as it exhibits a tensile modulus at a magnification within the range described above with respect to the tensile modulus of the fluoropolymer of the tube 30, but at least one selected from the group consisting of polyolefins and polyesters. One is preferred, at least one selected from the group consisting of polypropylene, polyethylene and polyethylene terephthalate is more preferred, and polypropylene is even more preferred.

The tensile elastic modulus of the non-fluoropolymer forming the holding member 23 of the injection device 20 is 1.2 times or more the tensile elastic modulus of the fluoropolymer of the tube 30 . It is preferably 1.3 times or more, more preferably 1.5 times or more, still more preferably 1.7 times or more, and most preferably 2.0 times or more, because fitting becomes easier. is.

The tensile modulus of the non-fluoropolymer forming the retainer member 23 of the injector 20 is compared to the tensile modulus of the fluoropolymer of the tube 30 from the standpoint of providing sufficient strength for the retainer member 23 of the injector 20. , The magnification is within the range described above, and is preferably 360 MPa or more, more preferably 600 MPa or more, still more preferably 800 MPa or more, particularly preferably 1000 MPa or more, and preferably 2000 MPa or less. , more preferably 1500 MPa or less.

Tube 30 is made of a fluoropolymer. By setting the tensile elastic modulus of the fluoropolymer forming the tube 30 to 300 MPa or more, the tube 30 can be easily inserted into the fitting portion 24 of the holding member 23 formed of the non-fluoropolymer. The tensile modulus of the fluoropolymer forming the tube 30 is preferably 350 MPa or more, more preferably 400 MPa or more, and still more preferably 450 MPa or more, because the insertion of the tube 30 becomes easier, It is particularly preferably 500 MPa or more, most preferably 550 MPa or more, preferably 1000 MPa or less, more preferably 800 MPa or less, and still more preferably 750 MPa or less.

The tensile elastic modulus of non-fluoropolymers and fluoropolymers was measured by placing pellets of these polymers in a mold, setting them in a press heated to 200 to 300 ° C., and melt-pressing at a pressure of 3 MPa to obtain a thickness of 2 mm. Non-fluoropolymer and fluoropolymer sheets are obtained respectively. Then, using each obtained sheet, it can be specified by measuring the tensile modulus under conditions of 25° C. and 50 mm/min according to ASTM D638.

The inner peripheral surface 25 of the fitting portion 24 of the holding member 23 is provided with unevenness, thereby providing pressure contact force between the outer peripheral surface 31 of the tube 30 and the inner peripheral surface of the fitting portion 24 of the holding member 23 . is higher, and the tube 30 can be fixed to the injection device 20 more firmly. In FIG. 2, a plurality of annular protrusions are provided on the inner peripheral surface 25 of the fitting portion 24 of the holding member 23, but the shape of the protrusions and recesses is not limited to this. The height from the bottom point of the concave portion to the peak of the convex portion in the uneven shape is preferably 0.005 mm or more, more preferably 0.01 mm or more, and still more preferably 0.02 mm or more. Moreover, the height from the bottom point of the concave portion to the peak of the convex portion in the uneven shape is preferably half or less of the thickness of the tube 30 . If the height of the convex portion is too small, the pressure contact force may not be increased sufficiently, and if it is too large, the tube 30 may bend during insertion.

An outer peripheral surface 31 at one end of the tube 30 is provided with irregularities, which further increases the pressure contact force between the outer peripheral surface 31 of the tube 30 and the inner peripheral surface 25 of the fitting portion 24 of the holding member 23. As a result, the tube 30 can be fixed to the injection device 20 more firmly. In FIG. 2, a plurality of annular protrusions are provided on the outer peripheral surface 31 at one end of the tube 30, but the shape of the protrusions and recesses is not limited to this.

In one embodiment of the connection structure, only one of the inner peripheral surface 25 of the fitting portion 24 of the holding member 23 and the outer peripheral surface 31 at one end of the tube 30 can be provided with unevenness. , the pressure contact force between the outer peripheral surface 31 of the tube 30 and the inner peripheral surface 25 of the fitting portion 24 of the holding member 23 is further increased. Moreover, both the outer peripheral surface 31 of the tube 30 and the inner peripheral surface 25 of the fitting portion 24 of the holding member 23 may be provided with unevenness. The unevenness is preferably provided only on the side of the holding member 23 having a high tensile elastic modulus. This improves the insertability of the tube and increases the pressure contact force between the tube and the holding member, so that the tube 30 can be fixed to the injection device 20 more firmly. In one embodiment of the connection structure, as shown in FIG. 2, unevenness can be provided on the inner peripheral surface 25 of the fitting portion 24 of the holding member 23. The engagement allows the tube 30 to be secured to the injector 20 .

The inner diameter of the fitting portion 24 of the holding member 23 is preferably configured to be smaller than the outer diameter of the tube 30 by 0.5% or more. By making the inner diameter of the fitting portion 24 of the holding member 23 sufficiently smaller than the outer diameter of the tube 30, the pressure contact force between the outer peripheral surface 31 of the tube 30 and the inner peripheral surface 25 of the fitting portion 24 of the holding member 23. is higher, and the tube 30 can be fixed to the injection device 20 more firmly.

After the tube 30 is inserted into the holding member 23, it is preferably held by the holding member 23 with a force of 3N or more, more preferably 5N or more, and more preferably 8N or more. It is more preferable to hold with a force of 11 N or more, most preferably a force of 11 N or more, and preferably a force of 25 N or less. Too little holding force can cause the tube to slip out during use, and too much can cause the tube to buckle during insertion.

The holding force of the tube is the holding force when the tube held by the holding member is removed from the holding member using a digital force gauge FGP series (FGP-5) manufactured by Nidec-Shimpo Corporation and a jig that clamps the tube. It can be determined by measuring the force maxima at room temperature.

The outer diameter of the tube 30 is not particularly limited, but is preferably 0.5 to 5.0 mm, more preferably 1.0 to 3.0 mm, still more preferably 1.2 to 2.0 mm, Most preferably 1.4 to 1.8 mm. The thickness of the tube 30 is not particularly limited, but is preferably 0.05 to 0.8 mm, more preferably 0.1 to 0.6 mm, still more preferably 0.3 to 0.5 mm. .

As shown in FIG. 3 , the tube 30 can be provided with a notch 32 at one end. As a result, the tube 30 can be more easily elastically deformed, making it easier to insert the tube 30 into the fitting portion 24 of the holding member 23, and further suppressing bending of the tube 30 during insertion. can be done. The number and position of notches are not particularly limited. For example, as shown in FIG. 3, two pairs of notches may be provided perpendicular to each other. Also, a pair of notches may be provided so as to face each other. The depth of the notch is preferably 0.1 mm or more, more preferably 0.2 mm or more, and preferably 3 mm or less. If it is too shallow, the effect of suppressing bending may be reduced, and if it is too deep, the holding force may decrease.

Only one end of the tube 30 may be provided with a notch, and the one end provided with the notch may be inserted into the fitting portion 24 of the holding member 23. can be manufactured, the tube 30 may be provided with notches not only at one end but also at the other end.

The container body 11 is preferably transparent enough to allow the liquid 12 contained therein to be visible. The liquid 12 contained in the transparent container has a refractive index of 1.35 to 1.41. Such liquids include, for example, liquid fragrances. Liquid fragrances are liquids containing fragrance-diffusing ingredients, usually containing perfume ingredients. A liquid fragrance is constituted by, for example, appropriately blending a perfume component that constitutes a base note, a perfume component that constitutes a middle note, or a perfume component that constitutes a top note. Liquid fragrances are classified into, for example, perfume extract, perfume, eau de toilette, eau de cologne, aftershave, and the like, depending on the content of perfume ingredients. The refractive index can be measured using an Abbe refractometer at 25° C. using a sodium D line as a light source.

Next, tube 30 will be described in more detail. The present disclosure also relates to tubes that can be easily secured to fittings of moldings formed from non-fluoropolymers.

As described above, the container body 11 of the spray container 10 shown in FIG. 1 contains the liquid 12 having a refractive index of 1.35 to 1.41. part is immersed in the liquid 12 . The liquid 12 in the container body 11 is sucked up to the injection device 20 through the tube 30 and is injected from the injection port 22 of the injection device 20 .

The tube 30 is made of a fluoropolymer having a tensile modulus of elasticity of 300 MPa or more. And a degree of transparency is imparted to the tube 30 .

Here, a liquid fragrance, which is an example of a liquid having a refractive index of 1.35 to 1.41, is stored in a transparent container equipped with a spray pump or a dispenser pump and sold to general consumers as a fragrance product. It is often done. The spray pump and the dispenser pump are provided with a tube for supplying the liquid fragrance to the spray pump and the dispenser pump (a tube for circulating the liquid fragrance), and such a tube is immersed in the liquid fragrance. It is stored in a transparent container together with the liquid fragrance. Fragrance products containing liquid fragrances are preferred to have an excellent aesthetic appearance due to the nature of the product. , low visibility, i.e., being difficult to see, in particular being virtually invisible (at first glance, tubeless and invisible unless looked at carefully); desired.

The present disclosure also relates to tubes for passing liquids having a refractive index between 1.35 and 1.41, and by appropriate selection of the fluoropolymer composition, the tubes immersed in liquids can be substantially It can be invisible and the aesthetics of the product with the tube immersed in the liquid can be excellent.

Although the refractive index of the fluoropolymer is not particularly limited, it is preferably 1.35 to 1.41, more preferably 1.355 or more, still more preferably 1.36 or more, and more preferably 1.40. or less, more preferably 1.39 or less, and particularly preferably 1.38 or less. The refractive index of the fluoropolymer in this range allows the tube to be nearly invisible or not visible when immersed in a liquid with a refractive index between 1.35 and 1.41; The aesthetics of the overall product to which the assembly of the present disclosure is attached can be enhanced. The refractive index of a fluoropolymer can be measured using an Abbe refractometer at 25° C. using a sodium D line as a light source, and can be measured using a fluoropolymer sheet produced by the following method.

(Method for producing fluoropolymer sheet)
Each fluoropolymer pellet is placed in a mold with a diameter of 120 mm, set in a press heated to 240 to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to form a fluoropolymer with a thickness of 1.5 mm. get a sheet.

The haze value of the fluoropolymer is not particularly limited, but is preferably 30% or less, more preferably 25% or less, still more preferably 22% or less, still more preferably 19% or less, and particularly preferably is 16% or less, most preferably 12% or less, preferably 0.01% or more, more preferably 0.05% or more, and still more preferably 0.1% or more. With the haze value of the fluoropolymer in this range, the resulting tube has high transparency and low visibility. Additionally, the tube can be made nearly invisible or completely invisible when immersed in a liquid with a refractive index of 1.35 to 1.41, resulting in an overall product to which the assembly of the present disclosure is attached. Aesthetics can be enhanced. The haze value of the fluoropolymer can be measured according to ASTM D1003 using a haze meter on the fluoropolymer sheet produced by the above method.

The transmittance of light having a wavelength of 400 nm of the fluoropolymer is preferably 50% or more, more preferably 65% or more, still more preferably 73% or more, particularly preferably 78% or more, and most preferably It is 80% or more, preferably 98% or less. The light transmittance of the fluoropolymer in this range results in a highly transparent and less visible tube. Additionally, the tube can be made nearly invisible or completely invisible when immersed in a liquid with a refractive index of 1.35 to 1.41, resulting in an overall product to which the assembly of the present disclosure is attached. Aesthetics can be enhanced. The transmittance of light having a wavelength of 400 nm of the fluoropolymer can be measured at a wavelength of 400 nm using a spectrophotometer for the fluoropolymer sheet produced by the above method.

The tube is preferably non-soluble in acetone. The insolubility of the tube in acetone makes the tube and assembly less susceptible to deterioration, even when the tube and assembly are immersed in liquids such as liquid fragrances for extended periods of time. Therefore, for example, even when a tube with excellent transparency is used, the transparency of the tube can be maintained for a long period of time, and the appearance of the fragrance product can be improved even when the fragrance product is used by repeatedly refilling the container with the liquid fragrance. Excellent aesthetics are maintained for a long period of time.

The solubility in acetone can be confirmed by a tube immersion test in acetone, which will be described later. A tube is said to be insoluble in acetone if the acetone immersion test of the tube does not cause dissolution and the tube retains its original shape.

In the present disclosure, when the tube is formed of two or more fluoropolymers, the tensile strength, refractive index, haze value and light transmittance of the fluoropolymers described above are measured for a mixture of two or more fluoropolymers. value.

The melt flow rate (MFR) of the fluoropolymer is preferably 3 to 150 g/10 min, more preferably 5 g/10 min or more, still more preferably 8 g/10 min or more, particularly preferably 12 g/10 min. min or more, more preferably 150 g/10 min or less, still more preferably 80 g/10 min or less, even more preferably 70 g/10 min or less, particularly preferably 60 g/10 min or less, Most preferably, it is 50 g/10 minutes or less. When the melt flow rate is within this range, it is possible to effectively suppress the occurrence of melt fractures during tube molding, thereby increasing the visibility or reducing the visibility due to light refraction caused by unevenness caused by the occurrence of melt fractures. deterioration can be effectively suppressed, and as a result, the resulting tube can be made less visible. In particular, since the melt flow rate is within the above range, the occurrence of melt fracture can be effectively suppressed even when the tube is formed at a relatively high speed or when the tube is formed into a small diameter tube. There is, and this can also contribute to the improvement of productivity.

The melt flow rate of a fluoropolymer can be measured using a melt indexer according to ASTM D1238. Setting values such as measurement temperature and load may be determined with reference to individual fluoropolymer standards (eg, ASTM D 2116).

The content of the fluoropolymer in the tube is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 98% by weight or more, particularly preferably 99% by weight or more, and most preferably 100% by weight. That is, it is most preferred that the tube consists essentially of fluoropolymer. In this case, it may contain an extremely small amount of unavoidably contained impurities.

Examples of fluoropolymers include ethylene/tetrafluoroethylene [TFE] copolymer, ethylene/tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer, polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [ CTFE] copolymer, vinylidene fluoride [VdF]/tetrafluoroethylene [TFE] copolymer, tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer, tetrafluoroethylene [TFE]/hexafluoro A propylene [HFP]/vinylidene fluoride [VdF] copolymer and the like are included.

The fluoropolymer contains ethylene units or HFP units and TFE units, as it can make the visibility of the resulting tube sufficiently low and impart the required tensile modulus to the tube. and at least one fluoropolymer selected from the group consisting of polymers containing VdF units, copolymers containing ethylene units and TFE units, and polymers containing VdF units. more preferably at least one fluoropolymer selected from the group consisting of coalescence, more preferably at least one selected from the group consisting of ethylene/tetrafluoroethylene [TFE] copolymers and VdF/TFE copolymers, Most preferred is at least one selected from the group consisting of ethylene/TFE/HFP copolymers and TFE/HFP/VdF copolymers.

Ethylene/TFE/HFP copolymers are copolymers containing ethylene units, TFE units and HFP units. The ethylene/TFE/HFP copolymer preferably contains 30 to 70 mol% of ethylene units, 20 to 55 mol% of TFE units and 1 to 30 mol% of HFP units, and 33 to 60 mol% of ethylene units and TFE units. It more preferably contains 25 to 52 mol % and 4 to 25 mol % HFP units, more preferably 35 to 55 mol % ethylene units, 30 to 47 mol % TFE units and 8 to 20 mol % HFP units.

The ethylene/TFE/HFP copolymer preferably further contains monomer units of ethylenically unsaturated monomers (excluding ethylene, TFE and HFP). The content of the monomer units of the ethylenically unsaturated monomer may be 0.1 to 10 mol%, or may be 0.1 to 5 mol%, relative to the total monomer units. , may be from 0.2 to 1 mol %, and may be from 0.3 to 0.8 mol %.

The ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with ethylene, TFE and HFP, and the ethylenically unsaturated monomer represented by the following formulas (1) and (2) It is preferably at least one selected from the group consisting of monomers (excluding ethylene, TFE and HFP).

Formula ( ¹ ): ^CX1X2 ₌ CX3 ⁽ _CF2 ) ^nX4
(Wherein, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8.)

Formula (2): CF ₂ =CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.)

Examples of ethylenically unsaturated monomers represented by formula (1) include CF ₂ =CFCl and the following formula (3):
_CH2 =CF-(CF2) _nX4 ⁽ ₃ )
(Wherein, X ⁴ and n are the same as above), and the following formula (4):
_CH2 =CH-(CF2) _nX4 ⁽ ₄ )
(Wherein, X ⁴ and n are the same as above.)
It is preferably at least one selected from the group consisting of CF ₂ =CFCl, CH ₂ =CFCF ₃ , CH ₂ =CH-C ₄ F ₉ , CH ₂ =CH-C ₆ F ₁₃ and CH ₂ ═CF—C ₃ F ₆ H, preferably at least one selected from the group consisting of CF ₂ ═CFCl, CH ₂ ═CH—C ₆ F ₁₃ , CH ₂ ═CFCF ₃ , and CH ₂ ═ More preferably, it is at least one selected from CF--C ₃ F ₆ H, CH ₂ ═CF--C ₃ F ₆ H (that is, 2,3,3,4,4,5,5-heptafluoro -1-pentene (CH ₂ =CFCF ₂ CF ₂ CF ₂ H) is particularly preferred.

Examples of ethylenically unsaturated monomers represented by formula (2) include the group consisting of CF ₂ =CF-OCF ₃ , CF ₂ =CF-OCF ₂ CF ₃ and CF ₂ =CF-OCF ₂ CF ₂ CF ₃ At least one more selected is preferable.

A TFE/HFP/VdF copolymer is a copolymer comprising TFE units, HFP units and VdF units. Since the TFE/HFP/VdF copolymer has excellent flexibility and transparency when the VdF content is high, the copolymerization ratio (mol% ratio) of TFE/HFP/VdF is 25 to 75 mol% of the TFE unit, It preferably contains 1 to 15 mol% of HFP units and 24 to 70 mol% of VdF units, more preferably 30 to 55 mol% of TFE units, 3 to 14 mol% of HFP units and 34 to 65 mol% of VdF units. , 30-40 mol % of TFE units, 3-12 mol % of HFP units and 50-65 mol % of VdF units. In addition, the TFE/HFP/VdF copolymer may contain 0 to 20 mol% of other monomer units, more preferably 0 to 10 mol%, and 0 to 5 mol%. is more preferred.

Other monomers are not particularly limited as long as they are copolymerizable with TFE, HFP and VdF, but ethylenically unsaturated monomers represented by the following formulas (5) and (6) (however, , TFE, HFP and VdF are excluded).
Formula ⁽ 5): ^CX11X12 = ^{CX13 (} _CF2 ) _qX14
(Wherein, X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are the same or different and represent H, F, Cl or Br, and q represents an integer of 0 to 8.)

Equation (6): CF ₂ = CF-ORf ⁴
(In the formula, Rf ⁴ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.)

As the other monomer, at least one selected from the group consisting of the ethylenically unsaturated monomers represented by the above formulas (5) and (6) (excluding TFE, HFP and VdF) perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), chlorotrifluoroethylene, 2-chloropentafluoropropene, perfluorinated vinyl ethers such as CF ₃ OCF ₂ fluorine-containing monomers such as perfluoroalkoxy vinyl ethers such as CF ₂ CF ₂ OCF=CF ₂ ), perfluoroalkyl vinyl ethers, perfluoro-1,3-butadiene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, and At least one monomer selected from the group consisting of alkyl vinyl ethers is more preferred, and perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether) and perfluoro(propyl vinyl ether) are most preferred.

In addition, since the TFE/HFP/VdF copolymer has excellent chemical resistance when the VdF unit content is low, the copolymerization ratio (mol% ratio) of the TFE unit, the HFP unit and the VdF unit is TFE/HFP/VdF = 45 to 95/0.1 to 15/0.1 to 45, more preferably 45 to 85/1 to 15/5 to 45 (molar ratio), 45 to 75/2 to 15/10 to 45 (molar ratio) is more preferred, and 45 to 70/5 to 15/20 to 45 (molar ratio) is most preferred. In addition, the TFE/HFP/VdF copolymer may contain 0 to 20 mol% of other monomer units, more preferably 0 to 10 mol%, and 0 to 5 mol%. is more preferred. As the other monomer, at least one selected from the group consisting of the ethylenically unsaturated monomers represented by the above formulas (5) and (6) (excluding TFE, HFP and VdF) perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), chlorotrifluoroethylene, 2-chloropentafluoropropene, perfluorinated vinyl ethers such as CF ₃ OCF ₂ Fluorine _- containing monomers such as _{CF2CF2OCF =} CF2), perfluoroalkyl vinyl ethers, perfluoro-1,3-butadiene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, _CF2 ═CHBr, CH ₂ ═CH—CF ₂ CF ₂ Br, CF ₂ ═CFBr, CH ₂ ═CH—CF ₂ Br, and at least one monomer selected from the group consisting of alkyl vinyl ethers, and perfluoro (methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether) are most preferred.

In the present disclosure, the content ratio of each monomer unit in the fluoropolymer can be calculated by appropriately combining NMR and elemental analysis, for example, according to the type of monomer units constituting the fluoropolymer.

The tube may be made of one type of fluoropolymer, or may be made of two or more types of fluoropolymers. The two or more fluoropolymers may be two or more fluoropolymers containing different types of monomer units, or two or more types containing the same type of monomer units at different content ratios. It may be a fluoropolymer, or two or more fluoropolymers containing the same type of monomer units in the same content ratio. The refractive index, haze value, light transmittance and tensile modulus of the fluoropolymer can be adjusted within the above ranges by appropriately selecting the type and content of the monomer unit of the fluoropolymer, the mixing ratio of the fluoropolymer, and the like. can be adjusted to give the fluoropolymer insolubility in acetone.

In particular, when two or more kinds of fluoropolymers are used, these characteristics can be improved by appropriately selecting the mixing ratio of the fluoropolymers without reviewing the monomer composition of the fluoropolymers used as materials from the polymerization stage. It can be more easily adjusted within the above range. It is also a preferred embodiment that the tube is made of two or more fluoropolymers, such as ethylene/TFE/HFP copolymer and TFE/HFP/VdF copolymer.

A suitable fluoropolymer when the tube is formed from one type of fluoropolymer is that the tensile modulus of the fluoropolymer is increased, and the tube can be more easily fixed to the fitting portion of the molded body. , an ethylene/TFE/HFP copolymer, a VdF/TFE copolymer (a copolymer consisting only of VdF units and TFE units), and a TFE/HFP/VdF copolymer, wherein the VdF unit content is , a copolymer containing 35 mol % or less of the total monomer units is preferred.

As a more suitable fluoropolymer when forming the tube from one type of fluoropolymer, ethylene/TFE/HFP copolymer is used because it can increase the tensile modulus of the fluoropolymer and impart insolubility to the tube in acetone. Preferred are copolymers and copolymers composed of TFE/HFP/VdF copolymers in which the content of VdF units is 35 mol % or less relative to the total monomer units.

As a more suitable fluoropolymer when the tube is formed from one type of fluoropolymer, the tensile modulus of the fluoropolymer is increased, and the refractive index, haze value and light transmittance of the fluoropolymer are easily adjusted to the ranges described above. Furthermore, since the tube can be made insoluble in acetone, an ethylene / TFE / HFP copolymer (a copolymer consisting only of ethylene units, TFE units and HFP units) containing HFP units Copolymers in which the amount is 17 mol% or more based on the total monomer units, and ethylene/TFE/HFP/other monomer copolymers, in which the total amount of HFP units and other monomer units is A copolymer having a content of 12 mol % or more based on the total monomer units is preferred.

A suitable combination of fluoropolymers when the tube is formed from two or more types of fluoropolymers is to increase the tensile modulus of the fluoropolymers so that the tube can be more easily fixed to the fitting portion of the molded body. From becoming
An ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer having an HFP unit content of 12 mol% or more and an ethylene/TFE/HFP/ethylenically unsaturated monomer having an HFP unit content of less than 12 mol% combination with a monomeric copolymer,
a combination of an ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer and an ethylene/TFE/HFP copolymer (a copolymer consisting only of ethylene units, TFE units and HFP units);
Combination of ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer and TFE/HFP/VdF copolymer Ethylene/TFE/HFP copolymer (copolymer consisting only of ethylene units, TFE units and HFP units combination) with a TFE/HFP/VdF copolymer is preferred.
The TFE/HFP/VdF copolymer may be a copolymer consisting only of TFE units, HFP units and VdF units, or may contain other monomer units as described above in addition to TFE units, HFP units and VdF units. It may be a copolymer containing.

The mixing ratio of each copolymer in the combination of ethylene/TFE/HFP copolymer and VdF/TFE copolymer (copolymer consisting only of VdF units and TFE units) is ethylene/TFE/HFP copolymer :VdF/TFE copolymer mass ratio is preferably 10:90 to 90:10, more preferably 30:70 to 85:15, still more preferably 45:55 to 85:15.

of each copolymer in a combination of an ethylene/TFE/HFP copolymer (a copolymer consisting only of ethylene units, TFE units and HFP units) and an ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer As a mixing ratio, the mass ratio of ethylene/TFE/HFP copolymer:ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer is preferably 10:90 to 99:1, more preferably 10:90 to 90:10, more preferably 30:70 to 70:30.

The mixing ratio of each copolymer in the combination of ethylene/TFE/HFP copolymer and TFE/HFP/VdF copolymer is: ethylene/TFE/HFP copolymer: mass of TFE/HFP/VdF copolymer The ratio is preferably 10:90 to 99:1, more preferably 10:90 to 90:10, more preferably 30:70 to 85:15, even more preferably 45:55 to 85 :15.

When the tube is formed from two or more fluoropolymers, a more suitable combination of fluoropolymers is to increase the tensile modulus of the fluoropolymer and to adjust the refractive index, haze value, and light transmittance of the fluoropolymer within the above ranges. can be easily adjusted, and the tube can be made insoluble in acetone,
a combination of an ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer and an ethylene/TFE/HFP copolymer (a copolymer consisting only of ethylene units, TFE units and HFP units);
An ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer and a TFE/HFP/VdF copolymer having a VdF unit content of 35 mol% or less and an HFP unit content of more than 10 mol% combination with coalescence (a copolymer consisting only of TFE units, HFP units and VdF units),
Ethylene/TFE/HFP copolymer (a copolymer consisting only of ethylene units, TFE units and HFP units) and a VdF unit content of 35 mol% or less and an HFP unit content of more than 10 mol% combination with a certain TFE/HFP/VdF copolymer (a copolymer consisting only of TFE units, HFP units and VdF units),
An ethylene/TFE/HFP/ethylenically unsaturated monomer copolymer and a TFE/HFP/VdF copolymer having a VdF unit content of 35 mol% or less and a TFE unit content of 55 mol% or more A combination with a coalescence (a copolymer consisting only of TFE units, HFP units and VdF units), wherein the mass ratio of ethylene / TFE / HFP copolymer: TFE / HFP / VdF copolymer is 45: 55 ~ which is 85:15;
combinations of ethylene/TFE/HFP/ethylenically unsaturated monomer copolymers and TFE/HFP/VdF/other monomer copolymers;
is preferred.

The tube is particularly a copolymer containing ethylene units, TFE units and HFP units, and the content of the HFP units is 17 mol% or more, more preferably 19.0, based on the total monomer units. It is preferable that it is formed of a copolymer of mol % or more because the balance of various properties is extremely excellent. Furthermore, by using such a copolymer, a tube having desired dimensions and shape can be easily obtained, and a tube having a low haze value and yellow index and a high tensile modulus can be easily obtained. can.

Accordingly, the present disclosure is a tube for passing a liquid having a refractive index of 1.35 to 1.41, which is a copolymer containing ethylene units, TFE units and HFP units, wherein the ethylene units and TFE The molar ratio of units (ethylene units/TFE units) is 38.0/62.0 to 70.0/30.0, and the content of HFP units is the total monomer units constituting the copolymer. It also relates to a tube containing a copolymer that is 1.0 to 30.0 mol % relative to the

The copolymers contained in the tubes of the present disclosure contain ethylene units (Et units), TFE units and HFP units.

In the copolymer contained in the tube of the present disclosure, the molar ratio (Et units/TFE units) is from 38.0/62.0 to 70.0/30.0, preferably 43.0/57.0 ~65.0/35.0, more preferably 47.0/53.0 to 62.0/38.0, still more preferably 51.0/49.0 to 58.0/42.0 and particularly preferably 52.0/48.0 to 56.0/44.0.

In the copolymer contained in the tube of the present disclosure, the content of HFP units is 1.0 to 30.0 mol %, preferably 10.0 mol %, based on the total monomer units constituting the copolymer. 0 to 27.0 mol%, more preferably 15.0 to 25.0 mol%, still more preferably 17.0 to 23.0 mol%, particularly preferably 19.0 to 21.0 in mol %.

The copolymers contained in the tubes of the present disclosure preferably further contain monomeric units of ethylenically unsaturated monomers, excluding ethylene, TFE and HFP. The content of the monomer units of the ethylenically unsaturated monomer may be 0.1 to 10 mol%, or may be 0.1 to 5 mol%, relative to the total monomer units. , may be from 0.2 to 1 mol %, and may be from 0.3 to 0.8 mol %.

The ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with ethylene, TFE and HFP, and the ethylenically unsaturated monomer represented by the following formulas (1) and (2) It is preferably at least one selected from the group consisting of monomers (excluding ethylene, TFE and HFP).

Formula ( ¹ ): ^CX1X2 ₌ CX3 ⁽ _CF2 ) ^nX4
(Wherein, X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8.)

Formula (2): CF ₂ =CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.)

Examples of ethylenically unsaturated monomers represented by formula (1) include CF ₂ =CFCl and the following formula (3):
_CH2 =CF-(CF2) _nX4 ⁽ ₃ )
(Wherein, X ⁴ and n are the same as above), and the following formula (4):
_CH2 =CH-(CF2) _nX4 ⁽ ₄ )
(Wherein, X ⁴ and n are the same as above.)
It is preferably at least one selected from the group consisting of CF ₂ =CFCl, CH ₂ =CFCF ₃ , CH ₂ =CH-C ₄ F ₉ , CH ₂ =CH-C ₆ F ₁₃ and CH ₂ ═CF—C ₃ F ₆ H, preferably at least one selected from the group consisting of CF ₂ ═CFCl, CH ₂ ═CH—C ₆ F ₁₃ , CH ₂ ═CFCF ₃ , and CH ₂ ═ More preferably, it is at least one selected from CF--C ₃ F ₆ H, CH ₂ ═CF--C ₃ F ₆ H (that is, 2,3,3,4,4,5,5-heptafluoro -1-pentene (CH ₂ =CFCF ₂ CF ₂ CF ₂ H) is particularly preferred.

Examples of ethylenically unsaturated monomers represented by formula (2) include the group consisting of CF ₂ =CF-OCF ₃ , CF ₂ =CF-OCF ₂ CF ₃ and CF ₂ =CF-OCF ₂ CF ₂ CF ₃ At least one more selected is preferable.

A tube can be produced by molding the above fluoropolymer into a tube shape. The method for forming the fluoropolymer into a tubular shape is not particularly limited, but the fluoropolymer can be produced by melt extrusion molding using an extruder. Specifically, an extruder equipped with a cylinder, a screw, a die head, and a die is used, the fluoropolymer is melted in the cylinder, and the melted fluoropolymer is extruded from the die into a tubular shape by rotating the screw. , thereby producing a tube.

The tubes described above can be used to carry liquids with refractive indices between 1.35 and 1.41. When the tube described above is made of a fluoropolymer whose tensile modulus is appropriately adjusted, it can be easily fixed to the fitting portion of the molding (retaining member of the injection device) having a large tensile modulus. can be done. Furthermore, when the tube is formed from a specific fluoropolymer, the tube can be made less visible, and thus can be suitably used for distributing liquid fragrances. The tube described above also constitutes a fragrance product comprising a transparent container for containing a liquid having a refractive index of 1.35 to 1.41, containing a liquid fragrance, and a tube for sucking up such liquid. In this case, the fragrance product can be made substantially invisible, thereby making the appearance excellent in aesthetics. . Furthermore, the present disclosure can also provide a container comprising a tube, and such a container is preferably a container for containing a liquid having a refractive index of 1.35 to 1.41, for example. be done.

The assembly and spray container described above can be used to contain liquids having refractive indices between 1.35 and 1.41 and to spray the contained liquids. The assembly and spray container described above also includes a transparent container body for containing a liquid having a refractive index of 1.35 to 1.41, including a liquid fragrance, and an assembly for sucking up and spraying such liquid. It can be suitably used as a fragrance product comprising. Further, if the tube is formed from certain fluoropolymers, the tube can be made less visible, thus allowing the fragrance product to have a tube that is virtually invisible, thereby reducing the appearance of the product. can be excellent in aesthetics.

Although the embodiments have been described above, it will be appreciated that various changes in form and detail may be made without departing from the spirit and scope of the claims.

Next, the embodiments of the present disclosure will be described with examples, but the present disclosure is not limited only to these examples.

Each numerical value in the examples was measured by the following method.

<Monomer Composition of Fluoropolymer>
Using a nuclear magnetic resonance apparatus AC300 (manufactured by Bruker-Biospin), ¹⁹ F-NMR measurement is performed at a measurement temperature of (the melting point of the polymer +20) ° C., and the monomer composition of the fluoropolymer is obtained from the integral value of each peak. rice field. Depending on the type of monomer, the monomer composition of the fluoropolymer may be determined by appropriately combining elemental analysis.

<Melt flow rate (MFR)>
The MFR of the fluoropolymers used in the examples was determined by the following method. According to ASTM D1238, using a melt indexer (manufactured by Yasuda Seiki Seisakusho), under a load of 5 kg, the mass of the copolymer flowing out per 10 minutes from a nozzle with an inner diameter of 2.1 mm and a length of 8 mm (g / 10 minutes ). The temperature for measuring the melt flow rate was determined to be 265° C. with reference to the individual fluoropolymer standard (ASTM D 2116).

(Method for producing fluoropolymer sheet)
A fluoropolymer pellet is placed in a mold with a diameter of 120 mm, set in a press heated to 240 to 300° C., and melt-pressed at a pressure of about 2.9 MPa to form a fluoropolymer sheet with a thickness of 1.5 mm. Obtained.

<Refractive index>
The refractive indices of the fluoropolymers and liquid fragrances used in the examples were measured using an Abbe refractometer (manufactured by Atago Optical Instruments Manufacturing Co., Ltd.) at 25° C. using a sodium D line as a light source. The refractive index of the fluoropolymer was measured using the fluoropolymer sheet produced by the above method.

<Haze value>
The haze values of the fluoropolymers used in the examples were determined by the following method. According to the method described above, the fluoropolymer pellets are molded into a sheet having a thickness of 1.5 mm, and the resulting sheet-shaped molding is measured using a haze meter (Haze Guard II manufactured by Toyo Seiki Co., Ltd.) according to ASTM D1003. Haze values were measured.

<Transmittance of light with a wavelength of 400 nm>
The transmittance of light having a wavelength of 400 nm for the fluoropolymers used in the examples was determined by the following method. According to the above method, the fluoropolymer pellets are molded into a sheet with a thickness of 1.5 mm, and the obtained sheet-shaped molded body is subjected to spectrophotometer U-4000 (manufactured by Hitachi, Ltd.) at a wavelength of 400 nm. Light transmittance was measured.

<Tensile modulus>
The tensile elastic moduli of the fluoropolymers and polypropylene used in the examples were determined by the following method. Fluoropolymer and polypropylene pellets are set in a mold, held at 200 to 300 ° C. for 15 to 30 minutes with a heat press, and after melting the polymer, compression molding is performed by applying a load of 3 MPa for 1 minute. Then, a sheet-shaped test piece having a thickness of 2 mm was produced. Then, the obtained sheet-shaped test piece was punched out to obtain a dumbbell-shaped test piece with a gauge length of 3.18 mm using an ASTM D638 Type V dumbbell. Using the obtained dumbbell-shaped test piece, using Autograph (manufactured by Shimadzu Corporation: AGS-J 5 kN), according to ASTM D638, under conditions of 50 mm / min, tensile modulus at 25 ° C. was measured.

(fluoropolymer)
In Examples and Comparative Examples, fluororesins having the monomer compositions and melt flow rates shown in Table 1 were used as fluoropolymers.

Abbreviations in Table 1 indicate the following monomers, respectively.
Et: ethylene TFE: tetrafluoroethylene HFP: hexafluoropropylene H2P: 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH ₂ =CFCF ₂ CF ₂ CF ₂ H)
VdF: vinylidene fluoride PPVE: perfluoro (propyl vinyl ether)

Examples 1-17 and Comparative Examples 1-3
Pellets of the fluororesin shown in Table 1 were charged into the hopper of an extruder (cylinder shaft diameter 20 mm, L/D=24) at the ratios shown in Tables 2 and 3. Using an extruder, extrusion molding was performed at a take-up speed of 2 m/min to obtain a tube having an outer diameter of 1.6 mm and an inner diameter of 0.8 mm. The temperature of the extruder cylinder and die was set at 160 to 300°C.

The following test was performed using the produced tube. The results are shown in Tables 2 and 3.

<Test for fitting the tube into the fitting portion of the holding member (insertability)>
A dispenser assembly to which a tube was connected was removed from a commercially available spray container (manufactured by Chanel, trade name: N°5) containing a liquid fragrance, and the tube was further removed from the dispenser assembly. The tubes prepared in Examples and Comparative Examples were inserted into the fitting portion (inner diameter: 1.5 mm) of the holding member (material: polypropylene, melting point: 165°C, tensile modulus: 1350 MPa) of the collected dispenser assembly, Evaluation was made according to the following criteria.
○: The tube can be inserted into the fitting part △: Sometimes the tube can be inserted into the fitting part, but sometimes the tube buckles and cannot be inserted into the fitting part ×: The tube buckles and does not fit into the fitting part cannot be inserted

<Immersion test of tube in liquid fragrance (non-visibility)>
The tubes prepared in Examples and Comparative Examples were immersed in a container containing liquid fragrance (manufactured by Chanel, trade name: N°5, refractive index of liquid fragrance: 1.371), and the background color was set to an RGB value of R = 255. , G=0 and B=0, the container was photographed from a distance of 50 cm in front of the container in the landscape mode of EOS KissX7 manufactured by Canon Inc., and the container reflected in the obtained image was observed and evaluated according to the following criteria.
◎: Existence of the tube can hardly be confirmed ○: Existence of the tube cannot be easily confirmed ×: Existence of the tube can be easily confirmed

<Immersion test of tube in acetone (insolubility)>
The tubes produced in Examples and Comparative Examples were immersed in acetone at room temperature for one week, and the tubes after immersion were observed and evaluated according to the following criteria.
○: The tube does not dissolve △: Part of the tube dissolves ×: The entire tube dissolves A tube with the result of this test being "○" can be said to be insoluble in acetone.

10 spray container 11 container body 12 liquid 20 injection device 21 injection button 22 injection port 23 holding member (molded body)
24 Fitting portion 25 Fitting portion inner peripheral surface 30 Tube 31 Tube outer peripheral surface 32 Notch

Claims (12)

An assembly comprising a tube for circulating a liquid having a refractive index of 1.35 to 1.41, and a molded body provided with a fitting portion for fitting one end of the tube,
wherein the molded article is made of a non-fluoropolymer, and the tube is made of a fluoropolymer having a tensile modulus of elasticity of 300 MPa or more;
The haze value of the fluoropolymer is 19% or less,
An assembly wherein said non-fluoropolymer has a tensile modulus of elasticity greater than or equal to 1.2 times the tensile modulus of said fluoropolymer. The injection device further comprises an injection device for injecting a liquid having a refractive index of 1.35 to 1.41, and the injection device is provided with a fitting portion for fitting the molded body to one end of the tube. 2. The assembly of claim 1, comprising as a retaining member. An assembly according to claim 1 or 2, wherein said fluoropolymer has a refractive index between 1.35 and 1.41. 4. The assembly according to any one of claims 1 to 3 , wherein the fluoropolymer has a transmittance of 50% or more for light with a wavelength of 400 nm. 1. The tube is made of at least one fluoropolymer selected from the group consisting of copolymers containing ethylene units and tetrafluoroethylene units and polymers containing vinylidene fluoride units. 5. The assembly according to any one of 4 . An assembly according to any preceding claim, wherein said tube is formed from two or more fluoropolymers having different monomer compositions. An assembly according to any preceding claim, wherein said tube is insoluble in acetone. The assembly according to any one of claims 1 to 7 , wherein said molded body is made of at least one non-fluoropolymer selected from the group consisting of polyolefins and polyesters. The assembly according to any one of claims 1 to 8 , wherein the inner peripheral surface of the fitting portion of the molded body is provided with unevenness. The assembly according to any one of claims 1 to 9 , wherein the inner diameter of the fitting portion of the molded body is smaller than the outer diameter of the tube by 0.5% or more. An assembly according to any preceding claim, wherein at least one end of said tube is provided with a notch. A fragrance product comprising an assembly according to any one of claims 1 to 11 and a container body.

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